1. Field of the Invention
The instant invention relates to improved processes for the preparation of polynucleate aluminum hydroxyl-halide complexes and of disinfectants. The instant invention obtains simplified processes for the preparation of polynucleate aluminum hydroxyl-chloride complexes, known as polynucleate aluminum compounds (PAC) and aluminum chlorohydrate (ACH), with ACH normally used to define products having basicities of over 50% and having a higher corresponding aluminum content. All of these complexes have the general formulation Alx(OH)yClz.
The instant invention also obtains simplified processes for the preparation of polynucleate metal hydroxy-halide complexes having the general formulation Mx(OH)yHaz, where Ha is a halogen, preferably Cl, and M is at least one metal or group of metals in either +2 or the +3 valence state and wherein, M is added to the polynucleate aluminum hydroxy-halide metal complex in the form of the metal halide acid solution, the base metal, the metal oxide or the metal hydroxide.
As defined in this instant invention, the term metal polymer (MP) is meant to refer to any polynucleate aluminum or polynucleate metal(s) complex or compound, including those which do not contain aluminum.
These MP are intended for use in liquid solids separations, such as in water purification, sludge dewatering and paper production, as well as solids dewatering and similar dewatering applications, being delivered in solution or in solid form. These MP can be used in a variety of applications including water purification, antiperspirants, corrosion control, and conductivity. The applications for these MP are only limited by the inclusion metal(s) and the application mechanism of the associated product, whether that product is in liquid, solid or dry form.
The instant invention obtains simplified processes for MP, wherein the halogen raw material is in a salt form and is converted to an acid form via either acidification with sulfuric acid (H2SO4) and/or sulfurous acid (H2SO3) or with electrolysis. The instant invention obtains improved processes for the manufacture of disinfectants, wherein the disinfectant contains an oxidative element or compound, and wherein the energy of manufacture is obtained from the energy of formation from at least one selected from a list consisting of: sulfur dioxide (SO2) from the burning of sulfur (S) in air or O2, sulfur trioxide (SO3) from the oxidation of SO2, H2SO4 formation from SO3, sulfurous acid (H2SO3) formation from SO2 with air or O2, halide acid formation from the reaction of a metal halide with an acid based upon an oxidation state of sulfur (a sulfoxy acid, preferably H2SO4 and/or H2SO3) and any combination therein. The instant invention obtains improved processes for the manufacture of an acid and a base, wherein said acid is based upon a halogen anion and wherein said base is based upon the hydroxyl anion. The instant invention provides for an improved process for the manufacture of gypsum, calcium sulfate di-hydrate, as well as: calcium sulfate, calcium sulfate ½ hydrate, calcium sulfite, calcium sulfite hydrate, and calcium hydrogen sulfite. The instant invention provides an economical and practical use for S, including the S removed from hydrocarbon fuels.
The processes of the instant invention: use less expensive raw materials, manage heat and chemical energy more efficiently, have lower transportation costs and require less handling of hazardous chemicals thereby requiring significantly less manufacturing cost.
2. Description of the Prior Art and Background
PAC—Since the 1970's it has been known in the art to prepare polynucleate (or polynuclear) aluminum complexes, also known as aluminum polymers. The first products that showed promise were poly aluminum sulfates. Processes for the production of poly aluminum sulfates are disclosed and presented in U.S. Pat. Nos. 4,284,611 and 4,536,665 and Canadian Patent Nos. 1,203,364; 1,203,664; 1,203,665; and 1,123,306, while used as a reference in this instant invention. In these patents, poly aluminum sulfate is produced by reacting sulfate solutions with sodium carbonate or sodium hydroxide to form an insoluble aluminum hydroxide gel, wherein soluble sodium sulfate is then removed.
U.S. Pat. No. 4,877,597 describes another process for the production of poly aluminum sulfate, while used as a reference in this instant invention. This process eliminated the initial step of producing an aluminum hydroxide gel by reacting aluminum sulfate with sodium aluminate.
U.S. Pat. No. 3,544,476 discloses a process for the formation of a poly aluminum chloral-sulfate, while used as a reference in this instant invention. It is prepared by first producing an aluminum chloride/aluminum sulfate solution and then basifying this solution with calcium carbonate of lime. The insoluble calcium sulfate is removed.
U.S. Pat. Nos. 2,196,016; 2,392,153; 2,392,153; 2,392,531; 2,791,486; 3,909,439, and 4,082,685 disclose processes for the production poly aluminum chloride (low basicity ACH), while used as a reference in this instant invention. These processes involve reacting aluminum oxy-hydrates or aluminum hydroxy-hydrates with hydrochloric acid (HCl) under high temperature and pressure conditions.
U.S. Pat. Nos. 4,362,643 and 4,417,996 disclose processes for the production of poly aluminum-iron complexes, while used as a reference in this instant invention. These processes involve reacting aluminum chloride/iron chloride solution with aluminum hydroxide or aluminum oxy-hydrates, as well as a poly aluminum chloride with iron.
U.S. Pat. No. 4,131,545 discloses a process for the production of poly aluminum sulfate compounds by reacting aluminum sulfate with phosphoric acid and calcium sulfate, while used as a reference in this instant invention. In the water industry, it is known at this time that PAC compounds containing sulfate are known to out perform aluminum salts, iron salts, PAC and ACH in water temperatures from approximately 34 (1° C.) to approximately 40° F. (4° C.).
The most common PAC is ACH. ACH is the most common PAC due to its higher aluminum content, which significantly increases the effectiveness of the PAC in operating temperatures over 40° F. (4° C.). U.S. Pat. Nos. 4,051,028 and 4,390,445 disclose processes for the formation of a poly aluminum hydroxychloride (ACH), while used as a reference in this instant invention. It is prepared by reacting aluminum chloride solution and aluminum hydroxide with calcium carbonate or lime. Insoluble calcium carbonate is removed. U.S. Pat. Nos. 4,034,067 and 5,182,094 disclose processes for the formation of a poly aluminum hydroxychloride, while used as a reference in this instant invention. It is prepared by reacting aluminum chloride solution with alumina or aluminum hydroxide under conditions of high temperature and pressure.
U.S. Pat. No. 5,938,970 discloses a method of forming polynucleate bi-metal hydroxide complexes (2 metals are used), while used as a reference in this instant invention. This process describes the use of a trivalent metal in combination with a divalent metal, wherein the trivalent metal is in an acid solution and is reacted with the oxide or hydroxide form of the divalent metal.
WO 97/11029 (PCT/US96/13977) and U.S. Pat. No. 5,985,234 disclose a method of forming polynucleate aluminum complexes, wherein sodium aluminate is required to be reacted with either aluminum chloride or aluminum chlorosulfate, while used as a reference in this instant invention; the reaction is carried out under conditions of high shear agitation to minimize gel formation. The reaction is to be carried out at a temperature of under 50° C. producing a milky suspension which clears over time.
At this time, ACH is known to be prepared by four methods. The first method is by reacting alumina and/or aluminum hydroxide with aluminum chloride solution (ACS) in a single step process at elevated temperature or pressure or both. Alumina is defined in the instant invention as any mixture comprising primarily aluminum oxy-hydrates and/or aluminum hydroxy-hydrates as those occur in nature and as purified from raw bauxite. Raw bauxite is purified by the Bayer process which utilizes the amphoteric nature of aluminum, which allows aluminum to be soluble at high pH as well as at low pH. Other metals do not exhibit this characteristic. Thereby aluminum is purified from other metals at a pH of approximately greater than 10.0 and at high enough operating temperature to flow the aluminum oxy- and hydroxy-hydrates. The second method is by reacting HCl with an excess of alumina and/or aluminum hydroxide at elevated pressure and/or temperature. The third process is by reacting alumina and/or aluminum hydroxide with HCl and metal carbonates or metal oxides at elevated temperature and/or pressure. The fourth method, which is disclosed in U.S. Pat. No. 5,904,856, presents a method of acidifying cement in HCl or ACS. A consequence of the second and the third process is large amounts of non-reacted aluminum hydroxide material that have to be returned to the process, which makes the process considerably more expensive. A consequence of the third process is a frothing of the carbonates in the reaction vessel; further, these products do not dry well should one desire a dry final aluminum polymer. The first and fourth processes are very expensive requiring the transport of large quantities of ACS. The second, third, and fourth processes are very expensive requiring the transportation of large quantities of HCl. Depending upon the concentration, HCl is at least approximately 65 percent water and ACS is at least approximately 60 to 90 percent water; therefore, the transportation of HCl or ACS requires the transportation and handling of large quantities of water and is therefore not economical. A consequence of the fourth process is the cost of first preparing the sintered cement containing Al2O3 and ClO. A consequence of all these processes is a purity limitation of the bauxite, if bauxite is used, as metal impurities in some forms of bauxite cannot be polymerized in the PAC when the PAC is used for drinking water purification.
All of these PAC and MP patent(s) are incorporated herein as a reference. All of these processes are limited with regard to the starting materials. Per any of these processes, large amounts of HCl or ACS or other metal acid solution must be handled. Per any of these processes, to prepare the ACS, HCl must be used. In summary, all require transportation, storage, and handling of large quantities of hazardous chemicals.
Further, the drinking water industry is placing restrictions on the amount of soluble aluminum in the final water product. Industrial processes have for years restricted aluminum salt coagulation to eliminate soluble aluminum in the final purified water. PAC(s) do not produce soluble aluminum in the final water. MP's do not place a soluble metal into the water. Due to requirements in both portable and industrial water coagulation, a safer, simpler and more economical process is needed for the manufacture of PAC(s) and MP(s).
Energy—None of these processes manage heat or chemical energy in an efficient manner. All of these processes require adding heat to the PAC or MP reactor and require heat in the preparation of alumina with no consideration given to the exothermic nature of either HCl or ACS formation. All of these processes require the preparation of HCl or delivery of HCl prior to ACS manufacture, while there are significant amounts of potential chemical energy available in the conversion of sodium chloride to HCl and in the conversion of aluminum to ACS utilizing HCl. Finally, none of these processes investigate either the use of H2SO4 and/or H2SO3 for the preparation of HCl, the very exothermic production of H2SO4 and/or H2SO3 from S or the very exothermic formation of HCl from a metal chloride salt reacting with H2SO4 and/or H2SO3, all of which present the ability to produce heat energy, steam and electricity.HCl—Other than the lost energy and the cost of purchase, HCl transportation has many issues, which include increased cost and environmental concerns. HCl has to be transported and suitable ventilation has to be arranged in order to eliminate the release of Hydrogen Chloride gas, HCl(g). Further, aqueous chlorine (Cl), or the chloride ion, is produced from aqueous HCl. The chlorine (Cl2) production process is an expensive one that requires drying and refrigeration prior to storage. The most significant issue with Cl2 is storage. Cl2 is an extremely hazardous chemical to store; therefore, storage of Cl2 is expensive. The hazardous nature of Cl2 has, in recent years, caused many water purification facilities to reevaluate the usage of Cl2 versus bleach or other disinfectants.
Upon contact with water, Cl2 forms both the chloride ion and the chlorite ion. The chlorite ions are decomposed into chloride ions with temperature. The addition of heat to large volumes of liquid is also very expensive. Moreover, HCl must be stored and transported in polymer-lined containers where the releases of HCl(g) vapors must be controlled. In summary, the production and transportation of HCl and/or Cl2 is both expensive and hazardous.
ACS—ACS is formed by the reaction of HCl with aluminum hydroxide, alumina (aluminum hydroxide and/or aluminum oxide in the dry or hydrate form) or aluminum. While ACS can be prepared from bauxite, this is not preferred in most applications because the acidification of aluminum in bauxite to ACS can also acidify any other metal impurities that may be present in the raw bauxite. Formation of ACS also releases HCl(g), which must be controlled. This is an expensive process. Therefore, in summary, the current processes always provide complications leading to increases in the cost of the final product, as well as many safety concerns which must be managed.Disinfectants and oxidants—Further yet, in all applications of water purification, there are efforts to eliminate the formation of chloro-organic compounds, which have been found to be at least one of: toxic, carcinogenic, teratogenic and any combination therein. The drinking water industry is limiting Cl2 and bleach disinfection, investigating alternative disinfectants such as H2O2, O2, ozone (O3) and chlorine dioxide (ClO2). The power industry has learned that those same chloro-organic compounds prematurely contaminate demineralizer beds, thereby resulting in the use of such alternative such as H2O2, O2, O3 and ClO2. The paper industry has learned that those same chloro-organic compounds are found in both the final paper product and in the plant wastewater, thereby requiring investigation of alternatives such as H2O2, O2 and O3. The manufacture of O3 requires O2, which is an expensive product formed by either separation of air or electrolysis of water. Also, ClO2 is an extremely hazardous chemical to transport, thereby requiring on-site generation from other Cl2 compounds, such as bleach (hypochlorite), chlorite and chlorate. Previous work in the manufacture of chlorite and chlorate is referenced herein in U.S. Pat. Nos. 2,092,944; 2,092,945; 2,194,494; 2,323,180; 2,616,783; 2,833,624; 3,101,248; 3,450,493; 3,760,065; 3,760,065; 3,828,097; 3,997,462; 4,081,520; 4,086,329; 4,087,515; 4,421,730; 4,465,658; 4,473,540; 4,683,039; 5,091,166; 5,091,167; 5,116,595; 5,205,995; 5,366,714; 5,593,653; 5,597,544; 5,639,559; and 6,251,357; along with 2189289 from CA; 55-098965 from JP and 56-92102 from JP. All of these patents are used as a reference to the instant invention.
While there are many methods to prepare H2O2, there are two primary chemical manufacturing processes: the hydroquinone (HQ) process and the sulfuric acid/electrolysis (SAE) process. Historically, SAE was the preferred process until the 1960's and 1970's wherein industry converted to HQ due to the operating cost savings of eliminating the electrical cost associated with SAE. However, by its nature, HQ has a limitation of organic contamination, which is due to the use of an organic chemical (hydroquinone) as a catalyst. Further, the discovery of chloro-organic toxicity has lead industry to require more pure forms of H2O2. In H2O2 manufacturing, membranes have been discussed as methods of H2O2 purification. U.S. Pat. Nos. 4,879,043 and 6,333,018 present the use of reverse osmosis membrane technology as a final purification step in the production of H2O2 manufactured by HQ, while used as a reference in this instant invention. U.S. Pat. Nos. 5,215,665; 5,262,058 and 5,906,738 present the use of reverse osmosis membrane technology in combination with cabonic resin technology as final purification steps in the production of H2O2 manufactured by HQ, while used as a reference in this instant invention. U.S. Pat. Nos. 5,851,042 and 6,113,798 present the use of converting contaminant particles by reacting said particles with micro-ligands, then separating said reaction products with membranes as a final purification step in the production of H2O2 manufactured by HQ, while used as a reference in this instant invention. U.S. Pat. No. 5,800,796 presents an electrochemical reactor wherein O2 and H2 are reacted across a conductive membrane containing reducing catalysts forming H2O2, while used as a reference in this instant invention. This process eliminates HQ while simplifying the process H2O2 production. However, the potential for contamination of H2O2 with heavy metals from the reducing catalyst is significant. Heavy metals contamination eliminates the potential use of H2O2 in either the production of micro-circuitry or water purification. In addition, the potential safety issues from the reaction of very explosive O2 and/or H2 in an electrolytic environment preclude the potential use of this process at the end-use site. U.S. Publication 20040126313 teaches the use of membrane technology in combination with SAE; however, a source of electricity is not presented. None of these references present SAE with a source of electricity. All of these H2O2 patents are incorporated herein as a reference.
While there are many methods to prepare O2, the separation of air into its component gases is performed by three methods: cryogenic distillation, membrane separation and pressure swing adsorption (PSA, which includes vacuum). Conventional cryogenic distillation processes that separate air into O2, Argon (Ar) and nitrogen (N2) are commonly based on a dual pressure cycle. Air is first compressed and is subsequently cooled, wherein cooling is accomplished by one of four methods: 1—vaporization of a liquid, 2—the Joule Thompson effect; 3—counter-current heat exchange with previously cooled warming product streams or with externally cooled warming product streams, and 4—the expansion of a gas in an engine doing external work. The cooled and compressed air is usually introduced into two fractioning zones. The first fractioning zone is thermally linked with a second fractioning zone which is at a lower pressure. The two zones are thermally linked such that a condenser of the first zone reboils the second zone. Air undergoes a partial distillation in the first zone producing a substantially pure N2 fraction and a liquid fraction that is enriched in O2. The enriched O2 fraction is an intermediate feed to the second fractioning zone. The substantially pure N2 from the first fractioning zone is used as reflux at the top of the second fractioning zone. In the second fractioning zone, separation is completed producing substantially pure O2 from the bottom of the zone and substantially pure N2 from the top. When Ar is produced or removed a third fractioning zone is employed. The feed to this third zone is a vapor fraction enriched in Ar which is withdrawn from an intermediate point in the second fractioning zone. The pressure of this third zone is of the same order as that of the second zone. In the third fractioning zone, the feed is rectified into an Ar rich stream which is withdrawn from the top, and a liquid stream which is withdrawn from the bottom of the third fractioning zone and introduced to the second fractioning zone at an intermediate point. Reflux for the third fractioning zone is provided by a condenser which is located at the top. In this condenser, Ar enriched vapor is condensed by heat exchange from another stream, which is typically the enriched O2 fraction from the first fractioning zone. The enriched O2 stream then enters the second fractioning zone in a partially vaporized state at an intermediate point above the point where the feed to the third fractioning zone is withdrawn.
The distillation of air, which is a ternary mixture into N2, O2 and Ar, may be viewed as two binary distillations. One binary distillation is the separation of the high boiling point O2 from the intermediate boiling point Ar. The other binary distillation is the separation of the intermediate boiling point Ar from the low boiling point N2. Of these two binary distillations, the former is more difficult, requiring more reflux and/or theoretical trays than the latter. Ar—O2 separation is the primary function of the third fractioning zone and the bottom section of the second fractioning zone below the point where the feed to the third zone is withdrawn. N2—Ar separation is the primary function of the upper section of the second fractioning zone above the point where the feed to the third fractioning zone is withdrawn. The ease of distillation is a function of pressure. Both binary distillations become more difficult at higher pressure. This fact dictates that for the conventional arrangement, the optimal operating pressure of the second and third fractioning zones is at or near the minimal pressure of one atmosphere. For the conventional arrangement, product recoveries decrease substantially as the operating pressure is increased above one atmosphere mainly due to the increasing difficulty of the Ar—O2 separation. There are other considerations, however, which make elevated pressure processing attractive. Distillation column diameters and heat exchanger cross sectional areas can be decreased due to increased vapor density. Elevated pressure products can provide substantial compression equipment capital cost savings. In some cases, integration of the air separation process with a power generating gas turbine is desired. In these cases, elevated pressure operation of the air separation process is required. The air feed to the first fractioning zone is at an elevated pressure of approximately 10 to 20 atmospheres absolute. This causes the operating pressure of the second and third fractioning zones to be approximately 3 to 6 atmospheres absolute. Operation of the conventional arrangement at these pressures results in very poor product recoveries due to the previously described effect of pressure on the ease of separation. Previous work to cryogenically separate air into its components can be referenced in U.S. Pat. Nos. 5,386,692; 5,402,647; 5,438,835; 5,440,884; 5,456,083; 5,463,871; 5,582,035; 5,582,036; 5,596,886; 5,765,396; 5,896,755; 5,934,104; 6,173,584; 6,202,441; 6,263,700; 6,347,534; 6,536,234; 6,564,581; 5,341,646; 5,245,832; 6,048,509; 6,082,136; 6,499,312; 6,298,668; and 6,333,445. All of these cryogenic patents are incorporated herein as a reference.
It is also well known in the chemical industry to separate air with membranes. Two general types of membranes are known in the art: organic polymer membranes and inorganic membranes. These membrane air separation processes are improved by setting up an electric potential across a membrane that has been designed to be electrically conductive. Previous work performed to separate air into its components with membranes can be referenced in U.S. Pat. Nos. 6,523,529; 6,761,155; 6,277,483; 5,820,654; 6,293,084; 6,360,524; 6,551,386; 6,562,104; 6,361,583; 6,565,626; 6,572,678; 6,572,679; 6,579,341; 6,592,650; 6,372,010; 5,599,383; 5,820,654; 5,820,655; 5,837,125; 6,117,210; 5,599,383; 5,902,370; 6,117,210; 6,139,810; 6,403,041; and 6,767,663. All of these membrane patents are herein incorporated by reference. While these patents present many innovations in membrane technology, none present use of a membrane wherein the energy of air separation is obtained from the formation energy of at least one selected from a list consisting of SO2 from the burning of S in air or O2, SO3 from the oxidation of SO2, H2SO4 formation from SO3, H2SO3 formation from SO2, halide acid formation and any combination therein.
It is also well known to separate air into O2 and N2 with PSA (herein to include vacuum swing adsorption). Previous work performed to separate air into its components with PSA can be referenced in U.S. Pat. Nos. 6,572,838; 6,761,754; 6,780,806; 3,793,931; 4,481,018; 4,544,378; 5,464,467; 5,810,909; 5,868,818; 5,885,331; 6,350,298; 6,171,370; 6,423,121; 6,649,556; 6,652,626; 4,013,429; 4,264,340; 4,329,158; 4,685,939; 5,137,548; 5,152,813; 5,258,058; 5,268,012; 5,354,360; 5,413,625; 5,417,957; 5,419,891; 5,454,857; 5,672,195; 6,004,378; 6,357,601; 6,321,915; 6,315,884; 6,298,664; 6,497,098; 6,510,693; and 6,516,787. All of these PSA patents are herein incorporated by reference. While these patents present many innovations in PSA technology, none teach wherein the energy of manufacture is obtained from the formation energy of at least one selected from a list comprising SO2 from the burning of S in air or O2, SO3 from the oxidation of SO2, H2SO4 formation from SO3, H2SO3 formation from SO2, halide acid formation and any combination therein.
An additional method for the manufacture of O2 is the electrolysis of water (H2O). Previous work in the electrolysis of H2O can be referenced in U.S. Pat. Nos. 6,723,220; 5,585,882; 6,572,759; 6,551,735; 6,471,834; 6,361,893; 6,338,786; and 6,336,430. All of these electrolysis patents are herein incorporated as reference. While these patents present many innovations in electrolysis technology, none present wherein the energy of manufacture is obtained from the energy of formation from at least one selected from a list comprising SO2 from the burning of S in air or O2, SO3 from the oxidation of SO2, H2SO4 formation from SO3, H2SO3 formation from SO2, halide acid formation and any combination therein.
It is well known in the art of methods and processes to manufacture oxides of halogens to form said halogen oxide from a metal halogen salt via electrolysis. While the most common metal is sodium, calcium is often used. While the most common halogen is chlorine, bromine, fluorine and iodine are often used. Previous work in the production of halogen oxide manufacture can be referenced in U.S. Pat. Nos. 5,342,601; 5,376,350; 5,409,680; 5,419,818; 5,423,958; 5,458,858; 5,480,516; 5,523,072; 5,565,182; 5,599,518; 5,618,440; 5,681,446; 5,779,876; 5,851,374; 5,858,322; 5,916,505; 5,972,196; 6,004,439; 6,203,688; 6,306,281; 6,436,435; 6,740,223; 6,761,872; 6,805,787; and 6,814,877. All of these patents in the preparation of an oxide form of a halogen are herein incorporated by reference. While these patents present many innovations in the production of halogen oxides, none present wherein the energy of manufacture is obtained from the energy of formation from at least one selected from a list comprising SO2 from the burning of S in air or O2, SO3 from the oxidation of SO2, H2SO4 formation from SO3, H2SO3 formation from SO2, halide acid formation and any combination therein.
Acid Manufacture (Sulfuric, Sulfurous and Hydrochloric)—HCl is known in the art to be produced by 2 processes, the Electrolysis Unit (EU) process and the Sulfuric Acid Process (SAP). The raw materials for EU production of HCl include sodium chloride, water, and electricity. The raw materials for SAP production of HCl include sodium chloride, H2SO4 and water.
Sulfuric acid has many forms and equivalents, all of which are based upon the sulfoxy (SxOy) anion moiety, wherein X can vary from 1 to 2 and Y can vary from 2 to 8. Examples would be sulfurous acid, sulfuric acid, oleum and persulfuric acid. As defined in this instant invention a sulfoxy acid is any proton donating acid containing a sulfoxy moiety. H2SO4 and H2SO3 are manufactured primarily by two competing processes, the condensation process and the contact process. In both cases, in a sulfuric acid plant, which will be herein after referred to as the sulfuric acid reactor (SAR), S is combusted in air and/or O2 to produce SO2. SO2 is then converted into SO3 in the contact process with the use of a catalyst, usually V2O5, in the presence of excess air at a temperature of about 400-450° F. (204-233° C.). In either process, SO3 can be slowly converted into H2SO4 by contact of said SO3 with H2O. In the condensation process, the combusted SO2 is contacted with H2O quickly forming H2SO3 and slowly forming H2SO4. In the contact process, said SO3 is contacted with H2SO4 forming H2S2O7 (oleum); oleum is then contacted with H2O forming 100 percent H2SO4. Often the oleum step is bypassed by directly reacting said SO3 with H2SO4 and H2O, thereby forming H2SO4. It is difficult to obtain 100 percent H2SO4 with the condensation process.
Bleach Manufacture—Bleach, a group IA or group IIA metal in solution with a hypohalite, is currently manufactured by two processes, electrolysis and acid/base blending. In electrolysis, a salt solution comprising a group IA or group IIA metal halide is placed in an electrolysis cell, wherein the salt is separated into the corresponding halide acid and the corresponding group IA or group IIA hydroxide, and wherein said halide acid and said group IA or group IIA hydroxide is allowed to mix, therein forming the corresponding group IA or group IIA metal in solution with the hypohalite while releasing hydrogen gas. In acid/base blending, a cold dilute solution of a group IA or group IIA metal hydroxide is mixed with either a halogen acid in aqueous form or with a halogen acid gas, wherein is formed the corresponding group IA or group IIA metal in solution with the hypohalite while releasing hydrogen gas. In all situations, concentration of the group IA or group IIA metal hypohalite in solution may be increased by adding an excess of a base, preferably the group IA or group IIA hydroxide until a concentration of about 15 percent of the group IA or group IIA metal hypohalite is obtained.
Under current manufacturing practices, the group IA or group IIA metal hydroxide used in the formation of a bleach is formed by the electrolysis of the corresponding group IA or group IIA salt in water. Therefore, the manufacture of any bleach is currently constrained by the cost and/or availability of electricity to perform electrolysis.
Previous work in the manufacture of a group IA or group IIA hydroxide are referenced herein in U.S. Pat. Nos. 3,976,556; 4,025,405; 4,100,050; 4101,395; 4,187,350; 4,221,644; 4,240,883; 4,295,944; 4,486,276; 4,586,994; 4,969,981; 6,488,833; along with A 1 067 215 from EP; 1120481 from EP; 55-89486 from JP; 1-234585 from JP; and 10-110287 from JP. All of these bleach patents are herein incorporated by reference.
Gypsum Manufacture—Gypsum, calcium sulfate di-hydrate, is a widely used product being the major component in the manufacture of wall-board or SHEETROCK (dry-wall). Gypsum is currently manufactured by three competing processes the mining of calcium sulfate di-hydrate, the hydration of mined calcium sulfate and the scrubbing of waste sulfoxy acid gases by an oxide of calcium, usually calcium oxide and/or calcium hydroxide. In all cases, the purity of manufactured gypsum is an issue. In the case of mined calcium sulfate and calcium sulfate di-hydrate, contaminants from the earth are an issue. And, in the case of scrubbing waste sulfoxy acid gases, impurities in the gas stream are often also oxidized and left in the gypsum product.
Previous work performed to purify a sulfoxy acid gas, thereby forming gypsum are herein referenced in U.S. Pat. Nos. 3,976,747; 4,312,280; 4,590,049; 4,782,772; 4,867,955; 4,915,920; 4,931,264; 5,006,323; 5,345,884; 5,538,703; 5,544,596; 5,551,357; 5,795,548; 5,814,288; 6,290,921; 6,309,996 and 6,912,962, along with foreign patents 40 39 213 from DE, 40 23030 from DE, 2 107207 from GB and 99/5822/6 from WO. All of these gypsum patents are herein incorporated by reference.
Transportation of Hazardous Chemicals and Sulfur Management—As population density increases, the transportation of hazardous chemicals, including acids and disinfectants, leads to an increased incidence of spills while the consequences of spills become more serious. While solutions of halide acid, hypohalite and halite are safer disinfectants for transportation, handling, and storage, the cost of manufacture of these disinfectants has limited their use. A more economical process is required for the manufacture of O2, ClO2, halide acid, hypohalite, and halate. In addition, while the US EPA is requiring the removal of sulfur from hydrocarbon fuels, thereby limiting atmospheric releases of oxides of sulfur from combustion exhaust, said removal is creating an abundance of sulfur, such that the petroleum refining industry is in need of a way to dispose of said abundance of sulfur.